An FTIR product study of the photooxidation of dimethyl disulfide     

I. Barnes  K. H. Becker  N. Mihalopoulos 《Journal of Atmospheric Chemistry》1994,18(3):267-289

The products of the 254 nm photolysis of ppm levels of DMDS have been studied as a function of the O₂ partial pressure at 760 Torr (N₂ + O₂) and 298±2 K. The major sulfur containing compounds detected were SO₂ and CH₃SO₃H (methane sulfonic acid, MSA) and the major carbon containing compounds were CO, HCHO, CH₃OH and CH₃OOH (methyl hydroperoxide). Within the experimental error limits the observed sulfur and carbon balances were approximately 100%. CH₃OOH has been observed for the first time in such a photooxidation system. Its observation provides evidence for the formation of CH₃ radicals by the further oxidation of the CH₃S radicals formed in the primary photolysis step.From the behavior of the DMDS photolysis products as a function of the O₂ partial pressure, O₃ concentration and added OH radical source it is postulated that the further reactions of CH₃SOH (methyl sulfenic acid), formed in the reaction OH + CH₃SCCH₃ CH₃SOH + CH₃S, are the main source of MSA in the 254 nm photolysis of DMDS.Some of the possible implications of the results of this study for the degradation mechanisms of other atmospherically important organic sulfur compounds, in particular DMS, are briefly considered.  相似文献   

Near UV absorption spectra and photolysis products of difunctional organic nitrates: Possible importance as NO x reservoirs     

Ian Barnes  Karl H. Becker  Tong Zhu 《Journal of Atmospheric Chemistry》1993,17(4):353-373

Difunctional organic nitrates are important products of the atmospheric reaction of NO₃ radicals with unsaturated hydrocarbons about which relatively little is known. In a continuation of the investigation of the atmospheric chemistry of such compounds, the UV absorption spectra of the following organic dinitrates and keto nitrates have been quantitively measured in the gas phase at 298±2 K and atmospheric pressure: 1,2-propandiol dinitrate, CH₃CH(ONO₂)CH₂(ONO₂); 1,2-butandiol dinitrate, CH₃CH₂CH(ONO₂)CH₂(ONO₂); 2,3-butandiol dinitrate, CH₃CH(ONO₂)CH(ONO₂)CH₃;cis 1,4-dinitrooxy-2-butene, CH₂(ONO₂)CH=CHCH₂(ONO₂); 3,4-dinitrooxy-1-butene, CH₂(ONO₂CH(ONO₂)CH=CH₂; -nitrooxy acetone, CH₃COCH₂(ONO₂); 1-nitrooxy-2-butanone, CH₃CH₂COCH₂(ONO₂); 3-nitrooxy-2-butanone, CH₃CH(ONO₂)COCH₃.Although the UV spectra of the nitrates are all very similar in shape those of the keto nitrates are red-shifted compared to the dinitrates and in the spectral range of atmospheric interest (>290 nm) their absorption cross-sections are approximately a factor of 5 higher. The cross-sections of the dinitrates are a factor of 2 higher than those reported in the literature for the corresponding alkyl mononitrates.The UV absorption cross-sections of the difunctional nitrates were used in combination with solar actinic flux data to estimate photolysis frequencies and consequently atmospheric lifetimes for these compounds. The results indicate that for the saturated difunctional nitrates studied in this work photolysis will generally be somewhat some important than reaction with OH radicals as an atmospheric removal process. However, for unsaturated nitrates loss due to reaction with OH will dominate over photolysis as an atmospheric sink.Preliminary FT-IR analyses of the photolysis products of -nitrooxy acetone, 3-nitrooxy-2-butanone and 2,3-butandiol dinitrate using both mercury and fluorescent lamps indicate that NO₂ is released in the primary step. The further reactions of the radicals thus produced result in the formation of CO, aldehydes and PAN. The possible significance of the results for difunctional organic nitrate as reservoirs for reactive odd nitrogen NO _y in the atmosphere, especially during the night, is briefly discussed.  相似文献   

A Database for Volatile Organic Compounds     

K. Mannschreck  K. Bächmann  K. H. Becker  Th. Heil  R. Kurtenbach  M. Memmesheimer  V. Mohnen  A. Obermeier  D. Poppe  R. Steinbrecher  Th. Schmitz  A. Volz-Thomas  F. Zabel 《Journal of Atmospheric Chemistry》2002,42(1):281-286

The database for volatile organic compounds (VOC data base) was created with the aim of providing an overview of tropospheric hydrocarbon measurements. The data base contains 202 substances, for which atmospheric and useful kinetic data such as rate coefficients, photolysis frequencies, mixing ratios, emission data and ozone formation potentials are compiled from available literature. The database file can be downloaded without charge from http://www.physchem.uni-wuppertal.de/voc-database. Registered users will be informed about the appearance of updates.  相似文献   

Verification of the Contribution of Vehicular Traffic to the Total NMVOC Emissions in Germany and the Importance of the NO3 Chemistry in the City Air     

R. Kurtenbach  R. Ackermann  K. H. Becker  A. Geyer  J. A. G. Gomes  J. C. Lörzer  U. Platt  P. Wiesen 《Journal of Atmospheric Chemistry》2002,42(1):395-411

In 1997 and 1998 several field campaigns for monitoring non-methane volatile organic compounds (NMVOCs) and nitrogen oxides (NO_x) were carried out in a road traffic tunnel and in the city center of Wuppertal, Germany. C₂–C₁₀ aliphatic and aromatic hydrocarbons were monitored using a compact GC instrument. DOAS White and long path systems were used to measure aromatic hydrocarbons and oxygenated aromatic compounds. A formaldehyde monitor was used to measure formaldehyde. Chemiluminescence NO analysers with NO₂ converter were used for measuring NO and NO₂. The high mixing ratios of the NMVOCs observed in the road traffic tunnel, especially 2.9 ppbv phenol, 1.5ppbv para-cresol and 4.4 ppbv benzaldehyde, in comparison with themeasured background concentration clearly indicate that these compounds were directly emitted from road traffic. Para-Cresol was for the first timeselectively detected as primary pollutant from traffic. From the measured data a NMVOC profile of the tunnel air and the city air, normalised to benzene (ppbC/ppbC), was derived. For most compounds the observed city air NMVOC profile is almost identical with that obtained in the traffic tunnel. Since benzene originates mainly from road traffic emission, the comparison of the normalised emission ratios indicate that the road traffic emissions in Wuppertal have still the largest impact on the city air composition, which is in contrast to the German emission inventory. In both NMVOC profiles, aromatic compounds have remarkably large contributions of more than 40 ppbC%. In addtion, total NMVOC/NO_x ratios from 0.6 up to 3.0ppbC/ppb in the traffic tunnel air and 3.4± 0.5 in the city air of Wuppertal were obtained. From the observed para-cresol/toluene and ortho-cresol/toluene ratios in the city air, evidence was found thatalso during daytime NO₃ radical reactions play an important role in urban air.  相似文献   

Palaeoseismicity studies on end-Pleistocene and Holocene lake deposits around Basle, Switzerland   总被引：3，自引：0，他引：3  

Arnfried Becker  Colin A. Davenport  Domenico Giardini 《Geophysical Journal International》2002,149(3):659-678

  相似文献   

Phases d'érosion—comblement de la vallée de la Papenoo et volcanisme subrécent à Tahiti,en relation avec l'évolution des iles de la Société (Pacifique Sud)     

Michel Becker  Robert Brousse  Gerard Guille  Herve Bellon 《Marine Geology》1974,16(5):M71-M77

A detailed mapping and data from borings support the conclusion that there is a late lava flow inside the Papenoo valley, the main valley of Tahiti island. This last volcanic manifestation which took place 400,000 years ago came after the phase of erosion corresponding to the Illinoian glacial period. It is one of the four phases of erosion followed by filling observed in the cross section of the Papenoo valley.  相似文献   

Die Methodik der radioaktiven Quellen-Untersuchung     

Prof. Dr. A. Becker 《International Journal of Earth Sciences》1924,14(4):364-374

Ohne Zusammenfassung  相似文献   

Copepod grazing and its potential impact on the phytoplankton development in the Barents Sea   总被引：2，自引：0，他引：2  

ULF BÅMSTEDT  HANS CHRISTIAN EILERTSEN  KURT S. TANDE  DAG SLAGSTAD  HEIN RUNE SKJOLDAL 《Polar research》1991,10(2):339-354

Compiled data from published and unpublished sources on copepod grazing of the large-sized copepods in the Barents Sea give wide ranges in grazing rates. Approximate average values indicate daily rations of 7–18% for copepodite stages V and VI and considerably higher values for the earliest copepodite stages. It is demonstrated that individual variability in gut fullness of copepods from a given locality is typically very high and not closely related to variable food abundance or depth of occurrence. There is no diel feeding rhythm during the summer, and even when relating copepod grazing to a number of biotic and abiotic factors through stepwise linear regression analysis, much of the variability remains unexplained. It is suggested that feeding behaviour, food quality and feeding history of the copepods all play important roles as factors which regulate copepod grazing. Model simulations on the phytoplankton succession, using literature data on laboratory-determined growth characteristics for solitary cells and colonies of the prymnesiophyte Phaeocystis pouchetii and large diatoms, indicate that the extent of the mixed layer and selective grazing by zooplankton are important factors that may explain the occurrence of dense blooms of P. pouchetii colonies, frequently observed during the spring.  相似文献   

Rockfalls triggered by the ad 1356 Basle Earthquake     

A. Becker  C. A. Davenport 《地学学报》2003,15(4):258-264

In the Basle region of Switzerland we demonstrate that rockfall blocks can be dated accurately using the radiocarbon method. Soil beneath rockfall blocks containing organic macro‐remains was sampled at four cliff sites in the Tabular Jura south‐east of Basle. A lightweight drilling rig drills a 101‐mm‐diameter hole through rockfall blocks up to 6 m in height. A downhole sampler is used to recover soil samples from below the blocks. Eighteen radiocarbon dates on charcoal, wood, needles of conifers and organic macro‐remains from 11 blocks gave dates between 970 and 440 bp . Calibrated ages range between ad 1210 and ad 1450. These results, along with field observations and historical research, suggest that a large number of blocks toppled as rockfalls within a short time interval in the epicentral area of the ad 1356 Basle earthquake.  相似文献   

Growth kinetics of enstatite reaction rims studied on nano-scale,Part I: Methodology,microscopic observations and the role of water   总被引：1，自引：0，他引：1  

Ralf Milke  Ralf Dohmen  Hans-Werner Becker  Richard Wirth 《Contributions to Mineralogy and Petrology》2007,154(5):519-533

The kinetics of (Mg, Fe)SiO₃ pyroxene layer growth within silicate thin films with total thickness <1 μm was studied experimentally at 0.1 MPa total pressure, controlled fO₂ and temperatures from 1,000 to 1,300°C. The starting samples were produced by pulsed laser deposition. Layer thickness before and after the experiments and layer composition as well as microstructures, grain size and shape of the interfaces were determined by Rutherford back scattering and transmission electron microscopy assisted by focused ion beam milling. Due to the miniaturization of the starting samples and the use of high resolution analytical methods the experimentally accessible temperature range for rim growth experiments was extended by about 300°C towards lower temperatures. The thickness of the layers at a given temperature increases proprotional to the square root of time, indicating a diffusion-controlled growth mechanism. The temperature dependence of rim growth yields an apparent activation energy of 426 ± 34 kJ/mol. The small grain size in the orthopyroxene rims implies a significant contribution of grain boundary diffusion to the bulk diffusion properties of the polycrystalline rims. Based on microstructural observations diffusion scenarios are discussed for which the SiO₂ component behaves immobile relative to the MgO component. Volume diffusion data for Mg in orthopyroxene from the literature indicate that the measured diffusivity is probably controlled by the mobility of oxygen. The observed reaction rates are consistent with earlier results from dry high-temperature experiments on orthopyroxene rim growth. Compared to high pressure experiments at 1,000°C and low water fugacities, reaction rates are 3–4 orders of magnitude smaller. This observation is taken as direct evidence for a strong effect of small amounts of water on diffusion in silicate polycrystals. In particular SiO₂ changes from an immobile component at dry conditions to an extremely mobile component even at very low water fugacities.  相似文献